Method for reducing the viscosity of chlorinated rubber



Patented Apr. 3 0, 1940 METHOD FOR REDUCING THE VISCOSITY OF CHLORINATED RUBBER John" Merriam Peterson, Kennett Square, Pas, as-

signor to Hercules Powder Company, Wi

lm ngi ton, Del., a corporation of. Delaware No Drawing. Application March 11, 1938, g Serial No. 195,321

l 8 Claims. (01. 260-772) This invention relates to a method-forlreducing the viscosity of chlorinated rubben,

It is well known that rubber can be transformed to a chlorinated derivative thereof by treatment of the rubber with chlorine under various condiw tions, the chlorination usually beinglcarried out in a suitable solvent for rubber, such as carbon tetrachloride, or other solvent, which; does not react with the chlorine. Baworcrude rubber 10 when dissolved in a solvent, such as, for exam-' ple, carbonv tetrachloride, swells greatly and eventually formsa very .-viscous solution which contains only a small concentration of rubber and,-of course,,a high concentration; of solvent. In other words, raw or cruderubber is a highly polymerized product and consequently small con- .centrations thereof in a solvent produce very. Treatment of such a.

highly viscous. solutions. product with chlorine, for example, results, then viscosity.

For many purposes,: however, such as, for example, lacquers, paints, varnishes and the like,

it is impractical to use highly. viscous products 25 because to make such operable it is necessary to use large amounts of solvent, which is a serious economic disadvantage. I

In order top'repare chlorinated rubber of lower viscosities, various .methodshave been proposed heretofore ,forfza'ccomplishing this object. [It has been proposed .to produce chlorinated rubber, capable of formingsolutions .of low'viscosity, bydisaggregating rubber by working .on a milliand then chlorinating the disaggregated product. To disaggregate the rubber still further, themilled rubber, insolution in ,a suitable solvent, is-exposed to daylight, or to ultra-violet light. As an alternative to, or. in addition to the milling or mechanicaldisaggregation, of the rubber, it may be oxidized, and this rubber,'when dissolved in a suitable solvent, produces a solution of low viscosity. ,,The viscosity characteristic of. the

rubber-so produced depends tosome extent on the degree of oxidation thereof.,qChlorination of suchoxidized rubber 'produces a lowerviSQOsity not so treated.

Processes for obtaining chlorinated rubber of a low viscosity characteristic have been pen to the objection that the viscosity characteristic is 50 still considerable and higher than is desirable for many purposes. Furthermore, it is usually quite dificult to control a-chlorination process so thata method for reducing the viscosity of chlorinated rubber to the" desired extent by'treating chlorin- 20. in a chlorinated product also having a very high product than the chlorination of a similar rubber It is'the' object of'thi'sfinvention to ,provide ated rubber after ithas beensubstantially completed chlorinated.

I have found that the viscosity of chlorinated rubber, substantially completely chlorinated, may be reduced to thedesired .extent, and without appreciable further chlorinatiomby treating said chlorinatedrubber in solution in a suitable solvent therefor with chlorinerand -an oxygen-containing gas for a period of time necessary to give the product of predetermined, reduced viscosity. I am aware that rubber has been chlorinated with chlorine and-an oxygen-containing'gas, forexample, air, but the process in accordance with this invention differentiates from any process heretofore used because the chlorine and oxygen-,

containing gas are not'used for chlorinating rubher, but for reducing the viscosity characteristic of chlorinated rubber after it has, been substan tially completely chlorinated... I

In the practical adaptation of" my invention, the process of reducing the viscosity will preferably be carried out in asolventfor chlorinated rubber. or any other solvent for chlorinated rubber not affected by the chlorine or by the oxygen-containing gas may be used, among which are, for

example, ethylene dichloride and chloroform.

In proceeding in accordance with my invention substantially completely chlorinated rubber made according to any of the methods known for chlorinating rubber in solution in a solvent such as, for example, carbon tetrachloride,is treated with chlorine and an oxygen-containing gas, such as, for example, air, until a predetermined, reduced viscosity is obtained. The time that the chlorinated rubber is treated'with the air and chlorine will depend upon the viscosity desired. For example, to obtain a very low viscosity product the time during which the chlorinated rubber solution istreated with the 'air and chlorine will be longer than the time of treatment of the same chlorinated rubber solution to. obtain a product For this purpose, carbon tetrachloride.

of anint'ermediate viscosity. I have found that a mixture of the oxygen-containing gas, such as,

for example, air, or oxygen alone, and chlorine may be passed into the chlorinated rubber solution continuously, the chlorine maybe added intermittently to the air stream being passed into the chlorinated rubber'solution, or the chlorine and air may be alternately passed into the chlorinated rubber solution.

I have-found that my processmay be carried the gas mixture comprisingchlorine and an oxygen-containing gas may vary. between wide limits but for most practical purposesitxwill vary from about 40% to99.5% by weight. Concentrations of chlorine less than 40% by weight of the gas mixture are" suitable under certain conditions, but in general I prefer the range before stated. When reducing the viscosity of substantially completely chlorinated rubber with a mixture of, chlorine and air, I prefer that said mixture contain from about 70% to about 98 by weight of chlorine.

My viscosity reducing rocess may be carried out in the same apparatus in which the chlorination reaction is carried out andmay be made, if so desired, a continuation of the chlorination cycle, it being understood that this invention does not require nor depend upon the use of any particular form of apparatus. As illustrative of a practical procedure for carrying out this invention, I took a sample of chlorinated rubber completely chlorinated, dissolved it in carbon tetrachloride, and subjected this to my viscosity reducing treatment in the manner indicated in the following table. For this I used 200 g. of a chlorinated rubber solution in carbon tetrachloride.

Tem erature Time of i Chlorine Viscosity" of tr atment treatment flow flow cochius C'. H7s, CcJmin. Cc./min. Seconds Original sample untreated 625 *Determined on the 15% solution in carbon tetrachloride by noting the time that it takes an air bubble 1 cm. long to ascend through 50 cm. of the solution in a tube 7 mm. in diameter at a temperature of 0. Y

From the above table it is apparent that passing air alone into the chlorinated rubber solution is substantially without effect on the viscosity, the differences shown being of the order of accuracy of the viscosity determinations. Air plus chlorine, however, has a substantial viscosity reducing effect.

As further illustrative of the viscosity-reducing effect of chlorine-air mixtures, I took a sample of chlorinated rubber in carbon tetrachloride not quite completely chlorinated and passed chlorine and air into this solution continuously for 62 hours, taking out samples at various intervals to determine the progress of the reduction in viscosity. The results obtained are shown in' the following table.

Percent Time of treatment with chlorine and air, chlorine in Viscosity in hours chlorinated centipoises* rubber Original 63. 9 1, 413 1, 64. 3 526 65. 8 348 67. 9 224 68. 2 29 68. 9 21 69. 3 16 69. 2 15 69. 4 6. 4 68. 9 5. 6 69. 6 4. 0 69. 3 4. 0

*Determined in a 20% by weight solution in toluene at C.

From this table it is seen that chlorination is substantially completed after 12 hours of treatment. The 24 hour sample shows a chlorine con} tent of 69.3% and a viscosity of 16 centipoises and thereafter the chlorine content remains substantially the same but the viscosity undergoes a very marked reduction.

accordance withv this invention is particularly effective for producing chlorinated rubber with a viscosity less than 20 centipoises, the viscosity being determined in a 20% by weight solution in' toluene at 25 C.

It will be understood that broadly this invention relates to a process for reducing the viscosityof chlorinated rubber, substantially completely chlorinated, comprising treating said chlorinated rubber dissolved in a solvent therefor with chlorine and an oxygen-containing gas for a period of time depending upon the viscosity of the final product desired. It will further be understood that the examples given are byway of illustration only and that various modifications may be madetherein without departing from the scope of the invention.

Furthermore, it will be understood that in my process air, oxygen or any other gas containing uncombined oxygen may be used and will; hereinafter, be referred to as oxygen-containing gas.

What I claim and desire to protect by Letters Patent is: g a

1. A method for reducing the viscosity of substantially completely chlorinated rubber having a chlorine content of more than 68.9% which comprises. treating said chlorinated rubber in solution in a solvent therefor with chlorine and an oxygen-containing gas and continuing said treatment until a chlorinated rubber having a pre-determined reduced viscosity is obtained;

2. A method for reducing the viscosity of substantially completely chlorinated rubber having a chlorine content of more than 68.9% which comprises treating said chlorinatedv rubber, in

solution in a solvent therefor, continuously with a mixture of chlorine and an oxygen-containing gas and continuing the addition of said gas mixture until achlorinated rubber having a pro-deterrninedreduced Viscosity is obtained.

3. A method for reducing the viscosity of sub'-' stantially completely chlorinated rubber having a chlorine content of more than 68.9% which comprises treating said chlorinated rubber in solution in a solvent therefor, with an oxygencontaining gas 1 to which small amounts of chlorine are added at intervals and continuing said treatment until a chlorinated rubber having a pre-determinedreduced viscosity is obtained.

4. A method for reducing the viscosity of substantially completely chlorinated rubber having a chlorinefcontent of more than 68.9% which comprises treating said chlorinated rubber, in solution in a solvent therefor, alternately with an oxygen-containing gas and chlorine and continuing said treatment until a chlorinated rubber having a pre-determined reduced viscosity is obtained. 1 a I 5. A method for reducing the viscosity of substantially completely chlorinated rubber having a chlorine content of more than 68.9% which comprises treating said chlorinated rubber in solution in carbon tetrachloride with a mixture of chlorine and an oxygen-containing gas and a chlorine content of ,more than 68.9% which 7") comprises treating said chlorinated rubber in solution in a solvent therefor 'with a mixture of chlorine and an oxygen-containing gas, the amount of chlorine being from about 40% toabout 99.5% by Weight of said gas mixture and continuing the addition of said gas mixture until a chlorinated rubber having a pre-determined reduced viscosity is obtained.

' 7. A method for reducing the viscosity of sub-- stantially completely chlorinated rubber having a chlorine content of more than 68.9% which comprises treating said chlorinated rubber in solution in carbon tetrachloride with a mixture of chlorine and air, the amount of chlorine being centipoises.

from about 70% to about 98% by weight of said gas mixture, and continuing the addition of said I gas mixture until a chlorinated rubber having a pre-determined reduced viscosity is obtained.

8. A method for reducing the viscosity of substantially completely chlorinated rubber having .a chlorine content of more than 68.9% which comprises treating said chlorinated rubber in solution in carbon tetrachloride with a mixture of chlorine and air until a chlorinated rubber is obtained, having a viscosity less than about 20 JQMERRIAM PETERSON. 

